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CN1090665C - Magnetic recording binder containing aminoalkylphosphonate salt - Google Patents

Magnetic recording binder containing aminoalkylphosphonate salt Download PDF

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Publication number
CN1090665C
CN1090665C CN95103950A CN95103950A CN1090665C CN 1090665 C CN1090665 C CN 1090665C CN 95103950 A CN95103950 A CN 95103950A CN 95103950 A CN95103950 A CN 95103950A CN 1090665 C CN1090665 C CN 1090665C
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Prior art keywords
parts
carbon atom
magnetic
acid
resin
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CN95103950A
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CN1113513A (en
Inventor
C·J·阿米萨克斯
D·E·维茨帝
D·P·赫伯拉
L·C·多尔蒙
L·皮基欧帝
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Morton International LLC
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Morton International LLC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
    • C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6926—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
    • G11B5/62—Record carriers characterised by the selection of the material
    • G11B5/68—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent
    • G11B5/70—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer
    • G11B5/702—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer characterised by the bonding agent
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
    • G11B5/62—Record carriers characterised by the selection of the material
    • G11B5/68—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent
    • G11B5/70—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer
    • G11B5/702—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer characterised by the bonding agent
    • G11B5/7021—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer characterised by the bonding agent containing a polyurethane or a polyisocyanate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/90—Magnetic feature
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31609—Particulate metal or metal compound-containing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Paints Or Removers (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Magnetic Record Carriers (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

A magnetic recording medium is prepared by applying a magnetic coating composition onto a non-magnetic support and curing said composition, said coating composition containing ferromagnetic particles dispersed in a binder comprising a thermoplastic resin selected from the group consisting of polyurethanes and polyester wherein there is chemically bonded to said resin at least one aminoalkylphosphonate represented by the formula: wherein R1 and R2 are the same or different oxyalkyl radicals having from 2 to 12 carbon atoms, R3 is an alkylene radical having from 1 to 12 carbon atoms, or an aralkylene radical having from 7 to 10 carbon atoms R4 is an alkyl radical having from 1 to 12 carbon atoms, a cycloalkyl radical having from 5 to 12 carbon atoms, or an aryl radical having from 6 to 12 carbon atoms wherein the aryl radical may contain a halogen atom, a hydroxyl group, or an amino group, and M+ is a metal ion or an ammonium ion.

Description

The magnetic recording tackiness agent that contains the aminoalkyl phosphonate
Technical background
The present invention relates to by magnetic coating being applied over the magnetic recording medium that obtains on the non magnetic support, as tape or disk.
The production of general purpose tape and disk is such: make magneticsubstance in the middle of about 1 micron long ferromagnetic particle being scattered in the arborescens tackiness agent, it being coated on the polyethylene terephthalate film again.Outstanding dispersiveness is being provided, the orientation of charging efficiency and magnetic-particle and give outstanding wearing quality, wear resistance, thermotolerance, and the slickness of magnetisable coating and to the aspects such as adhesivity of support, the arborescens tackiness agent plays important effect.
The example of the arborescens tackiness agent of Shi Yonging has traditionally: vinylchlorid/vinyl acetate resin copolymer, vinylchlorid/vinyl-acetic ester/vinyl alcohol copolymer, vinylchlorid/vinylidene chloride multipolymer, urethane resin, vibrin, the acrylonitrile/butadiene multipolymer, Nitrocellulose, acetate butyric ester Mierocrystalline cellulose, Resins, epoxy, and acrylic resin.In these resins, traditional urethane resin is compared with other resin has outstanding toughness and wear resisting property, but usually relatively poor at aspect of performances such as antistick, heat-resisting and operation stabilities.For those reasons, the mixed system that often uses a kind of urethane resin and Nitrocellulose or vinylchlorid/vinyl acetate copolymer to form.After applying magnetic coating composition and drying, can use the polymeric polyisocyanate slaking, to improve the wearing quality of urethane, thermotolerance and bond properties by approximately under room temperature to 40 ℃ or higher temperature.
Magnetic recording layer with the intensity that is greatly improved and other performances has adopted a kind of binder resin, and it contains vinyl chloride copolymer (as vinylchlorid/vinyl-acetic ester/copolymer-maleic anhydride) and urethane resin.The Japanese Patent publication number No.59-8127 tell people, and polar group is mixed in the composition resin one or both, to improve the dispersiveness of ferromagnetic powder in this tackiness agent.
The wearing quality of conventional resins tackiness agent and wear resistance also are not enough to be used for video-tape, computer magnetic tape and diskette, and these need the occasion of high-performance and high reliability.More and more need high-density and high quality record medium, also need slickness simultaneously.Along with the increase of required slickness, running durability has been subjected to infringement, thereby must the higher resin glue of exploitation wearing quality.In order to realize this purpose, proposed multi-functional composition is introduced in the urethane, the latter can react with polymeric polyisocyanate; TriMethylolPropane(TMP) and diethanolamine are the representatives of this composition.One big shortcoming of this method is that when wearing quality increased, the dispersiveness of magnetic-particle usually descended.In recent years, high record density that magnetic medium is required and high quality are realized by the meticulous magnetic-particle that uses metal and barium ferrite, but concerning being used for these particulate resin glues, are still needed it that wearing quality and dispersiveness are arranged.
In Japanese Patent publication number No.57-3134 and 58-41564 and Japanese Patent publication number (kokai) No.61-48122, told about a kind of metal-salt by mixing metal sulfonate salt group or acid phosphorus compound to improve the method for particulate dispersiveness.Recently, people such as Yatsuka are at U.S patent No.5, have told about this multi-functional composition that exists in the hope of the resin that improves the coating wearing quality at the metal-salt that contains metal sulfonate salt group or acid phosphorus compound in 009,960 and have still caused less dispersiveness.Yatsuka also says, mixes the bicyclic amide acetal and can overcome defective in the prior art in urethane resin.A kind of preferred urethane contains a kind of metal-salt of acid phosphorus compound of following formula as functional group: Wherein M is an alkali metal atom; R 1It is the alkyl of 3-10 carbon atom; X is the functional group that forms ester; R 2Be the alkyl of 1-12 carbon atom, the cycloalkyl of 6-12 carbon atom can contain the aryl of the 6-12 carbon atom of halogen atom, hydroxyl, amino or an OM ' group (wherein M ' is an atoms metal).
The general introduction of invention
Based on this, the inventor keeps the mechanical property of tackiness agent in coating simultaneously in order to improve the dispersiveness of magnetic-particle in resin glue, has carried out extensive studies.The inventor finds, in being mixed with the adhesive resin of specific phosphorus compound, does not need the bicyclic amide acetal.
Therefore, one of purpose of the present invention provides a kind of resin glue that is used for ferromagnetic particle, and it has outstanding particles dispersed but can not contain the bicyclic amide acetal.
Two of purpose of the present invention provides a kind of such tackiness agent with high glass transition temperature.
Three of purpose of the present invention provides a kind of magnetic coating composition, and it has the dispersed of outstanding ferromagnetic particle and does not contain vinyl chloride-base polymer and the multipolymer of being with polar group.
Four of purpose of the present invention provides a kind of magnetic recording medium that contains this coating.
Five of purpose of the present invention provides a kind of new ionic phosphonate.
These and other purpose of the present invention can become clear in the following description, and they are accomplished by a kind of adhesive resin of the functional group that contains following formula:
Figure C9510395000061
R wherein 1And R 2Can be identical or different, for having the alkoxyl group of 2-12 carbon atom, R 3Be the alkylidene group of 1-12 carbon atom, or the inferior aralkyl of 7-10 carbon atom, R 4Be the alkyl of 1-12 carbon atom, the cycloalkyl of 5-12 carbon atom, or the aryl of 6-12 carbon atom, wherein aryl can contain a halogen atom, hydroxyl or amino, and M +Be metal ion or ammonium ion.Detailed Description Of The Invention
Binder resin of the present invention is urethane or polyester.Magnetic coating composition of the present invention can contain one or both in urethane and the polyester, but also can contain other adhesive resins, and is mentioned above as those.
Urethane resin of the present invention is that a kind of weight-average molecular weight is 3000-150,000, and be the how alcohol of 300-5000 by (A) molecular weight, (B) molecular weight is less than 1000 chain extension agent and (C) reaction of polymeric polyisocyanate and the resin that makes.Urethane can be section type block or the random copolymers that contains hard fragment and soft segment.The aminoalkyl group phosphate group of formula I may reside in two kinds of fragments or one of them.
Many alcohol (A) can be polyester glycols, polyether glycol, polycarbonate diol, pcl-diol acid lactone or wherein the two or whole mixtures.
The carboxylic acid composition of polyester glycol can be with aromatic dicarboxylic acid such as terephthalic acid, m-phthalic acid, phthalic acid or its acid anhydrides and 1,5-naphthalene diacid; Aromatic series hydroxyl carboxylic acid such as para-hydroxybenzoic acid are to (hydroxyl-oxethyl) phenylformic acid; Aliphatic dicarboxylic acid such as succsinic acid, hexanodioic acid, nonane diacid, sebacic acid and dodecandioic acid; Ester ring family's dicarboxylic acid such as cyclohexane dicarboxylic acid, hydrogenation 2,6-naphthalene dicarboxylic acids etc. is an example.
The glycol composition of polyester glycol comprises N, two (hydroxyalkyl) aminoalkyl phosphonic acid esters of N-, and formula I functional group is just derived thus and is got.The example of other glycol composition comprises ethylene glycol, propylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, neopentyl glycol, two sweet glycol, dipropylene glycol, 2-methyl isophthalic acid, ammediol, 2-butyl-2-ethyl-1, ammediol; 2,2,4-trimethylammonium-1,3-pentanediol; Cyclohexanedimethanol, the oxyethane of dihydroxyphenyl propane and propylene oxide adduct, the oxyethane of Hydrogenated Bisphenol A and propylene oxide adduct, polyoxyethylene glycol, polypropylene glycol, 1,4-butyleneglycol and analogue.The example that can be used for polyester glycol of the present invention that also can enumerate has: by lactone such as ε-caproic acid lactone ring opening polymerization and pcl-diol acid lactone.The Tone 0260 of Union Carbide is a kind of example of commercially available this class glycol.
The production of polyester glycol can be passed through traditional technology, and wherein acid is heated in the presence of acid catalyst with the compound that contains hydroxyl, reduces to about 10 or littler up to acid number.
The example of polyether glycol has polyoxyethylene glycol, and polypropylene glycol gathers 1, and 4-butyleneglycol and blended gather (propylene glycol/ethylene glycol), and especially those contain high kind to 20% (weight) ethylene oxide unit.All above-mentioned polyethers all can be buied.
Polycarbonate diol can PPG Industries, and the trade mark that Inc. provides is that 120 series and 140 series of Duracarb are example.
Derive the ionic phosphonic acid ester of formula I functional group, especially N, two (hydroxyalkyl) aminoalkyl phosphonic acid esters of N-, be to react by hydrogen phosphite dialkyl and N by the Mannich that improves, N-pair-hydroxyalkyl amine or hydroxyl aralkylamine and aldehyde react, and make with one of a kind of alkali soap phosphonate group again.M +Example be at N, two (2-hydroxyethyl) the aminomethyl phosphonates of N-, N, two (3-hydroxypropyl) the aminomethyl phosphonates of N-, N, two (4-hydroxyl butyl) the aminomethyl phosphonates of N-, N, two (4-hydroxyl butyl) the ciliatine salt of N-, [N-(2-hydroxyethyl), N-(3-hydroxypropyl)] sodium, potassium, lithium, ammonium, alkylammonium and quaternary ammonium ion in ciliatine salt and [N-(2-hydroxyethyl), N-(3-hydroxypropyl)] aminomethyl phosphonate.
Three function compositions are as 1,2, the 4-benzenetricarboxylic anhydride, and TriMethylolPropane(TMP), glycerine and analogue can use with bifunctional acid and glycol, but care should be used to is to keep its premium properties when preparation is used for the adhesive resin of magnetic medium.
Therefore, the application's urethane resin can have a kind of polyester, polyethers or polycarbonate main chain or its mixed backbone.The effect of chain extension agent (B) is a content of regulating urethano group in the urethane resin, gives resin with fastness.The example of chain extension agent comprises the straight chain glycol, as ethylene glycol; 1, ammediol; The 2-methyl isophthalic acid, ammediol; 2-butyl-2-ethyl-1, ammediol; 1, the 4-butyleneglycol; 1, the 6-hexylene glycol; Cyclohexanedimethanol, xylyl alcohol, glycol ether; Triglycol; Ethylene oxide adduct with dihydroxyphenyl propane; Branched glycol such as propylene glycol, neopentyl glycol, 1,2-butyleneglycol, 1,3 butylene glycol, 2,2,4-trimethylammonium-1,3-pentanediol; Propylene oxide adduct with dihydroxyphenyl propane; Water; Amino alcohol such as monoethanolamine and N-Mono Methyl Ethanol Amine; Diamines such as quadrol, hexanediamine and isophorone diamine are suitable in some cases, but for fear of crosslinked, preferably secondary amine such as N, N '-dialkyl benzene diamines; P, p '-two (alkylamino) ditane; Piperazine and analogue.The content part of chain extension agent is by the size and the character decision of chain extension agent, and part is by the desired performance decision that reaches.Three function chain extension agent such as TriMethylolPropane(TMP)s, diethanolamine, trolamine and glycerine also can use, but need be careful its influence to the urethane performance.
The example of polymeric polyisocyanate (C) has 2,4-toluylene vulcabond; 2,6-toluylene vulcabond; To the toluylene vulcabond; Diphenylmethanediisocyanate or MDI; Between inferior phenylene diisocyanate; Hexamethylene diisocyanate; 1,4-fourth vulcabond; 3,3 '-dimethoxy-4 ', 4 '-the Ya biphenyl diisocyanate; 2, the 4-naphthalene diisocyanate; 3,3 '-the inferior biphenyl of dimethyl-4,4 '-vulcabond; 4,4 '-the Ya biphenyl diisocyanate; 4,4 '-two isocyanic acid phenylbenzene ether-ethers, 1, the 5-naphthalene diisocyanate; Right-the Ya Xylene Diisocyanate; Between-the Ya Xylene Diisocyanate; 1,3-two isocyanato methylcyclohexanes; 1,4-two isocyanato methylcyclohexanes; 4,4 '-two isocyanato bicyclohexane; 4,4 '-two isocyanato dicyclohexyl methyl hydrides; Two isocyanic acid isophorone esters etc.Triisocyanate, as 2,4-toluylene vulcabond trimer and 1, oneself two isocyanic acid trimers of 6-etc. also can use, but need be careful it to the urethane Effect on Performance.
When production was used for urethane resin of the present invention, the mol ratio of isocyanic ester and hydroxyl should be 1: 2-1: in 1 the scope.This ratio is one of factor of determining the molecular resin amount.When isocyanate content was too big, the urethane that obtains was terminal with the isocyanic ester, and storage life is poor.When hydroxy radical content is excessive, molecular weight and molecular weight.The normal preferred proportion of NCO/OH is 1: 1 to 1: 1.2.The preferred weight-average molecular weight of urethane is 3000-150,000.When less than 3000 the time, the physical strength of urethane descends; When greater than 150,000 o'clock, soltion viscosity rises operation easier.
The polyaddition reaction that is used to produce urethane of the present invention can be a single step, wherein all compositions react simultaneously, also can be to use prepolymer method, wherein long chain diol at first reacts with excess isocyanate, and what obtain then is that terminal prepolymer is used the chain extension agent polymerization again with the isocyanic ester.Reaction can be carried out under fusion or solution state.The temperature that is fit to is about 120 ℃, about 90 minutes usually time.The block polymer method is the legal a kind of flexible method of pre-polymerization, and wherein the long-chain compound of another hydroxyl reacts with the prepolymer that with isocyanic acid ether is end.Stannous octoate, stannous oxalate, dibutyl tin laurate, triethylamines etc. can be used as catalyzer.UV light absorber, hydrolysis inhibitor, antioxidant and other useful additives can be before producing urethane, among or add afterwards.
The vibrin that is used as binder resin in magnetic coating composition of the present invention can similar polyester glycol (A), and just its weight-average molecular weight is between 3000-150000.
Be used for that the polyalcohols (A) of the preparation of urethane of the present invention and in the present invention-itself is as the vibrin of binder resin, the both is contained the aminoalkyl phosphonate of capacity, it provides the functional group of formula I, serves as about 5-about 1000 gram equivalents/1 * 10 to produce a kind of phosphonate concentration 6The tackiness agent of g polymkeric substance.
The ferromagnetic particle that is used for coating composition of the present invention comprises: the magneticmetal powder, and as iron, metal oxide such as γ-Fe 2O 3, γ-Fe 2O 3/ Fe 3O 4Mixed crystal, CrO 2And contain the ferric oxide of cobalt; Ferromagnetic alloy powder such as Fe-Co and Fe-Co-Ni; And barium ferrite.The ratio of suitable magnetic-particle/tackiness agent is about 3.5: 1 (weight ratio).Pigment such as carbon black and abrasive material such as aluminum oxide, green chromium (green chrome), and α-Fe 2O 3Also may reside in the coating composition.Wherein each granular size is 0.01-2 μ.
The normal solvent that uses in producing magnetic coating composition of the present invention.The example of wherein useful solvent comprises ketone such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK) and pimelinketone; Ester such as methyl acetate, ethyl acetate and ethyl butyrate; Glycol ether such as glycol monoethyl ether; Toluene, dimethylbenzene; The mixture of tetrahydrofuran (THF) and two or more above-mentioned solvents.
Softening agent, lubricant, dispersion agent, static inhibitor and other additive can join in the magnetic coating composition.The example of softening agent has phthalic acid dibutyl ester and triphenylphosphate.Dioctyl sodium sulfosuccinate, tertiary butyl benzoic acid polyvinyl ether, the ethyl naphthalene sodium sulfonate, sulfuric acid two lauryls, Zinic stearas, the soybean oil lecithin, tetradecanoic acid, butyl myristate, silicone oil are lubricant, the example of static inhibitor and dispersion agent.
Magnetic recording medium of the present invention comprises a non-magnetic substrate and by applying magnetic coating composition and dry and magnetisable coating that form thereon in substrate, and said composition contains the magnetic-particle that is dispersed in the tackiness agent as mentioned above.Base material comprises polyester, polypropylene, cellulosic triacetate, polycarbonate, poly-(vinylchlorid), and aluminium.The example of suitable poly terephthalic acid diethyl ester film is in U.S. Patent No. 4,454,312; 4,595,715; With 4,693, description is arranged in 932.Above-mentioned patent is incorporated herein by reference.
In equipment, ball mill is arranged, pebble mill, sand mill and high speed burrstone mill as the composition that disperses the magnetic coating composition.
The example of coating method of application has spread coating, the excellent coating method of silk, scraper coating method, anti-phase roller painting, roll squeezer coating method, rotogravure method.After magnetisable coating is applied over the non-magnetic substrate surface, films and in magnetic field, to stand directional process before the drying usually, and stand smooth treatment.About 1 micron-Yue 12 micron thickness of magnetisable coating and about 600-5000 Gauss's magnetic field is provided.
By means of mixing above-mentioned aminoalkyl phosphonate, binder resin of the present invention becomes the resin of homogeneous, has remarkable magnetic-particle dispersiveness.As a result, magnetic recording medium of the present invention, tackiness agent wherein contain the resin of at least a usefulness aminoalkyl phosphonate of the present invention modification, have outstanding filling properties and outstanding magnetic-particle orientation, and the outstanding smoothness of recording medium magnetosphere.
Adhesive resin of the present invention and magnetic coating composition will be set forth in the following example in detail.Wherein all proportions is calculated by weight, unless otherwise noted.Magnetic recording medium of the present invention be by add linking agent as the poly-isocyanide ester of three functions to the magnetic coating composition, again it is applied on the base band drying, and make by the traditional way slaking.
The present invention will more specifically be set forth in the following example.Wherein all proportions by weight, unless otherwise noted.All viscosity Brookfield method is used #2 axles are in 20rpm and 25 ℃ of measurements, unless otherwise mentioned.With 60 ° of angular measurement gloss.
Embodiment 1 ethyl-N, two (hydroxyethyl) aminomethyl phosphonic acids one sodium of N-
The preparation of this intermediate is by 256 parts of diethyl-N of adding in being furnished with the reactor that stirring is arranged of distillation column, and in the NaOH aqueous solution of two (hydroxyethyl) aminomethyl phosphonic acid esters to 14% (weight) of N-, slowly heated mixt makes by product ethanol begin distillation.Column temperature maintains 72-75 ℃, and temperature of reactor maintains 80 ℃ until the distillation end.The pH of cooled product is 10.1, and the percentage solids content is 51.7.
Embodiment 2
As another kind of method, ethyl-N, two (hydroxyethyl) aminomethyl Alendronate (hereinafter the being referred to as HAP) preparations of N-are by being furnished with condensation collection post, heating 849.5 parts of cyclohexanedimethanols (CHDM) in the reactor of thermometer and feed hopper, 129.2 the mixture of the diethyl phosphonate of part deionized water and 448.2 parts of embodiment 1 is to 60-65 ℃, with about 60-80 drip/minute the NaOH aqueous solution of speed adding 167.8 part 42.6% (weight).Holding temperature is lasted about 50 minutes 70-75 ℃ scope.After finishing adding NaOH, soon, cool the temperature to 72 ℃.Remove ethanol byproducts and aqueous solvent with distillation method, obtain containing the mixture of CHDM and 36% (weight) phosphonate of the present invention.
Embodiment 3
It with the OH value 205 first polyester, it is by 42.5 parts of CHDM, 20.2 part 2-butyl-2-ethyl-1, the reaction of ammediol (BEPD) and 37.2 parts of hexanodioic acids makes, with the OH value is that another polyester of 195 mixes, the latter is by 42.1 parts of CHDM, and the reaction of 20.0 parts of BEPD and 37.9 parts of hexanodioic acids makes.The OH value of the blend of the hard polyester that obtains is 198.The OH value of first " soft " polyester is 195, by 30 parts of butyleneglycols (BD), and the reaction of 23 parts of BEPD and 47 parts of hexanodioic acids and making.The OH value of second " soft " polyester is 205, by 30.3 parts of BD, and the reaction of 23.1 parts of BEPD and 46.6 parts of hexanodioic acids and making.The ethylene glycol solution of 50% (weight) HAP is mixed with the mixture of " firmly " and " soft " blend of 70/30 again, make the OH value increase to 250.The weight percent of every kind of composition is: 66.09% hard polyester, the glycol solution of 28.32% soft polyester and 5.59% phosphonate of the present invention.700 parts of these mixtures and 379.2 parts of ditan-4,4 '-two isocyanide esters (MDI) mix, and 120 ℃ of reactions 90 minutes, obtain urethane of the present invention.The viscosity of the methyl ethyl ketone solution of this urethane of 15% (weight) is 188cps.
Embodiment 4
Prepare the mixture of HAP and CHDM by the general procedure of embodiment 2, only be to use 566.3 parts of (39mol) fused CHDM, 298.8 parts of (1.2mol) phosphonic acid esters, 86.0 parts of water and 111.9 parts of NaOH solution.Add 10.0 parts of Irganox 1076 inhibitor, use nitrogen purging to help to remove the second alcohol and water.Then, add 1249.3 parts of CHDM again, be warming up to 80-90 ℃, and add 1169.2 parts of (8.0mol) hexanodioic acids.Carefully continue heating with oil bath, making the maximum temperature difference of bathing gentle reaction temperature compound is 35 ℃.In case the distillation beginning just stops nitrogen purging, and the reacting by heating mixture was kept 5 hours to the highest 195-200 ℃.Pressure is reduced to about 45-50mmHg, kept reaction mixture 1 hour in 195-200 ℃ again.Column temperature maintains 50 ℃.Stop distillation by adding 0.25 part of stannous oxalate, and be depressurized to 20-25mmHg again, holding temperature is at 195-200 ℃ simultaneously, until acid number less than 1.The OH value of product is 187.9.
Repeat this program, just the CHDM that adds for the second time is 9.7mol.The acid number that obtains is 0.78, and the OH value is 214.1.The preparation polyurethane/polyurea
Preparation OH value is the blend of two kinds of polyester of 187.9 and 214.1, and making its OH value is 198.Part blend (38.9 parts) is that 198 polyester mixes with other two kinds of OH values again, i.e. CHDM/MP glycol/adipate polyester (155.5 parts) and MP glycol/adipate polyester (194.4 parts).The MP glycol is the 2-methyl isophthalic acid, ammediol.Add 78 parts of N again to this blend, N '-dibutyl phenylenediamine, mixture react with 252.2 parts of MDI again.The viscosity of the methylethylketone of its 15% (weight) (MEK) solution is 20cps, and the viscosity of the MEK/ pimelinketone (CHO) of its 15% (weight)/toluene mixture (1: 1: 1) w solution is 32cps.
Embodiment 5
The phosphine acidifying polyester blend of embodiment 4 mixes by 15: 85 weight ratio with the MP glycol/adipate polyester among this embodiment, adds the MP glycol again as chain extension agent.The amount of every kind of composition is respectively 199.5,1130.9 and 69.6 parts.Add 759.3 parts of MDI in this mixture, reaction was carried out 90 minutes.The viscosity of the MEK solution of 15% urethane is 24cps, and when containing 20% solid, viscosity is 62cps.15% MEK/CHO/ toluene mixture (1: 1: 1) of urethane wThe viscosity of solution is 40cps.
Embodiment 6
Press the general procedure of embodiment 5, just the amount of MDI reduces to 754.4 parts.The viscosity of each solution is respectively 34cps, 100cps, and 58cps.
Embodiment 7 and 8 magnetic coating compositions
The preparation binder solution, it contains 181 parts of vinylchlorid, vinyl alcohol and vinyl-acetic ester contain sodium sulfur-bearing multipolymer, for the article number of Nippon Zeon company is Zeon MR-110, it respectively is 341.8 parts of MEK that solvent is served as reasons, the solvent that CHO and toluene are formed is used for the mill base (millbase) that its prescription is shown in table 1.
Table 1
Composition Weight
Cobalt improved ferric oxide 1900.0
Carbon black 152.0
Aluminum oxide 38.0
Methylethylketone 635.8
Pimelinketone 496.1
Toluene 635.8
Tetradecanoic acid 14.3
Binder solution (15% total solids) 1206.4
With barreling mill mill base batching on probation among the KDL.Before grinding, use #It is 5500 that 6 axles record Brookfield viscosity at 20rpm.After the grinding, viscosity is 12600.
Contain respectively the polyurethane solution A of product of 271.4 parts of embodiment 5 and embodiment 6 and B at solvent (by the MEK that respectively is 512.7 parts, CHO and toluene are formed) in make, prepare in the magnetic coating composition deposit fluid prescription of embodiment 7 and 8 by following method being used for:
In every kind of described polyurethane solution, add 109.4 parts of MEK, 20.5 parts of CHO, 109.4 parts of toluene and 14.25 parts of butyl myristates make deposit solution (let-down solution) C and D.
Embodiment 7 and 8 magnetic coating preparation of compositions are: with deposit solution C and D deposition mill base, using deposition factor is 40.63 parts/100 parts mill bases respectively.
Embodiment 9 and comparative example 1
Mill base tackiness agent of the present invention prepares as follows:
The Alendronate solution that in 566.3 parts of (3.9mol) fused CHDM, adds 608.3 parts of embodiment 1,0.25 part of stannous oxalate catalyzer and 1169.2 parts of hexanodioic acids.Temperature maintenance stops the 195-200 ℃ of distillation until water.Then, after 140-150 ℃, add 1249.3 parts of CHDM again, be warming up to 195-200 ℃ again in reaction mixture.When distillation when stopping again, pressure is reduced to 45-50mmHg, reaction continued 1 hour in same temperature again, keep simultaneously column temperature in 50 ℃ so that the loss of CHDM is reduced to minimum.Add 0.5 part of catalyzer again, pressure is reduced to 20-25mmHg, finishes reaction at 195-200 ℃, can be reached by acid number to be about 1 and show.The OH value is 189.6.Prepare urethane of the present invention.
(the OH value is 205 to mix first polyester, from by 42.5%CHDM, 20.2%BEPD, the reaction mixture of forming with 37.2% hexanodioic acid (being weight ratio) makes) and second polyester (the OH value is 195, from forming but ratio is 42.1: 20.0: 37.9 a reaction mixture makes) by same composition thus acquisition OH value is 198 blend.By 868.8 parts of above-mentioned phosphine acidifying polyester, 372.4 parts of described polyester blends and 158.8 parts of mixture and 738.1 parts of MDI reactions that BEPD forms form urethane of the present invention.Molecular weight determination shows, the MW of product wBe 18,800; MW NBe 7200; MW zBe 32,000.The viscosity of 15%MEK solution is 420cps.The MEK/CHO/ toluene (1: 1: 1) of same concentration wThe viscosity of solution is 142cps.The comparative example 1
The tackiness agent of prior art, the article number of Nippon Zeon company is the vinylchlorid of Zeon MR-110, the sodium that contains of vinyl alcohol and vinyl-acetic ester contains the sulphur multipolymer.Binder solution
The preparation of above-mentioned polyurethane solution of the present invention and comparative example's 1 binder solution is to make by 95.4 parts of tackiness agents of dissolving in mixed solvent respectively.This mixed solvent contains MEK, and CHO and toluene respectively are 179.9 parts.The mill base construction
Binder solution is used in the mill base prescription as shown in table 2.
Table 2
Composition Weight
Cobalt improved ferric oxide 1000.0
Carbon black 80.0
Aluminum oxide 20.0
Methylethylketone 334.6
Pimelinketone 261.1
Toluene 334.6
Tetradecanoic acid 7.5
Binder solution 15% solid 634.9
Before grinding, the Brookfield viscosity of the mill base that is made into of embodiment 9 is used #6 axles are measured as 4100cps in 20rps.After in KDL, grinding in the mill on probation, be 8750cps.
Before grinding, the Brookfield viscosity of comparative example 1 the mill base that is made into is used #6 axles are measured as 4950cps in 20rpm.After in KDL, grinding in the mill on probation, be 7550cps.
5 times by behind the sand mill, the dispersive ability of the mill base of embodiment 9 (representing) with gloss, coercive force (Hc), (Switching Field Dis-tribution SFD) lists in table 3 for squareness ratio (SR) and switch yard distribution.
Table 3
Number of pass times MB Gloss Hc SR SFD
1 9 53 740 0.79 0.42
CE1 51 739 0.77 0.44
2 9 91 747 0.81 0.41
CE1 88 749 0.81 0.40
3 9 103 748 0.82 0.40
CE1 92 743 0.81 0.40
4 9 108 746 0.81 0.40
CE1 96 741 0.81 0.40
5 9 110 748 0.82 0.40
CE1 99 740 0.81 0.40
Embodiment 10
The Alendronate solution that in 566.3 parts of (3.9mol) fused CHDM, adds 608.3 parts of embodiment 1,0.25 part of stannous oxalate catalyzer and 1169.2 parts of hexanodioic acids.Temperature maintenance stops the 195-200 ℃ of distillation until water.Then, after 140-150 ℃, add 1249.3 parts of CHDM again, be warming up to 195-200 ℃ again in reaction mixture.When distillation when stopping again, pressure is reduced to 45-50mmHg, reaction continued 1 hour in same temperature again, keep simultaneously column temperature in 50 ℃ to reduce to the loss of CHDM minimum.Add 0.5 part of catalyzer again, pressure is reduced to 20-25mmHg, finishes reaction at 195-200 ℃, can be reached by acid number to be about 1 and show.The OH value is 189.6.Preparation urethane
By 620.6 parts of phosphine acidifying polyester that so make, 620.6 parts of OH values are the polyester of MP glycol/hexanodioic acid of 194.7 and mixture that 158.9 parts of BEPD form and 758.4 parts MDI reacts, and form urethane of the present invention.Molecular weight determination shows that the MWw of product is 20,431, and MWn is 8888; MWz is 33351.The viscosity of 15%MEK solution is 25cps.The viscosity of MEK/CHO/ toluene (1: 1: 1) the w solution of same concentration is 44cps.
Embodiment 11
(the OH value is 195 to mix first polyester, from by 30% butyleneglycol CHDM, 23%BEPD, the reaction mixture of forming with 47% hexanodioic acid (being weight ratio) makes) and second polyester (the OH value is 205, from by 30.3% butyleneglycol, the reaction mixture that 23.1%BEPD and 46.6% hexanodioic acid (weight ratio) are formed makes) thus obtaining the OH value is 198 blend.625.8 part this polyester blend, 625.8 parts of embodiment 10 described phosphine acidifying polyester and 154.8 parts of mixture and 758.5 parts of MDI reactions that BEPD forms form another kind of urethane of the present invention.Molecular weight determination shows that the MWw of product is 21,691, and MWn is 7563; MWz is 38,123.The viscosity of 15%MEK solution is 1200cps.The viscosity of MEK/CHO/ toluene (1: 1: 1) the w solution of same concentration is 162cps.The comparative example 2
Morton International, the Morthane CA-398 urethane that Inc. sells, this is a kind of tackiness agent of prior art.It does not contain functional group, and weight-average molecular weight is 73,800, and number-average molecular weight is 29,500.
Embodiment 12-16
Embodiment 10 and 11 and comparative example 2 in the deposit solution of binding agent according to following formulated:
MEK 327.4
CHO 280.6
TOL 327.4
BuMyr * 7.5
Tackiness agent 142.9
1085.8
* BuMyr=butyl myristate
Mill base among embodiment 9 and the comparative example 1 all uses 40.6 parts of deposit solution/100 part mill bases to deposit.Magnetic oxide: the ratio of tackiness agent is 3.50: 1.Deposition composition is deposited on the thick poly terephthalic acid diethyl ester film of 36 μ m, and it is thick that dry back forms 4 μ m.The composition of the present invention and prior art is as follows:
Embodiment
The deposit fluid of mill base+embodiment 10 of 12 comparative examples 1
The deposit fluid of mill base+embodiment 10 of 13 embodiment 9
Mill base+comparative example's 2 of 14 embodiment 9 deposit fluid
The deposit fluid of mill base+embodiment 11 of 15 comparative examples 1
The deposit fluid of mill base+embodiment 11 of 16 embodiment 9
The performance of these compositions is listed in table 4, and wherein viscosity table is shown VIm (viscosity at once) and VOv (the back viscosity of spending the night), and dispersive ability represents that with gloss coercive force is Hc, and squareness ratio is SR, and switch yard is distributed as SFD.Coercive force is the quantity of the magnetic of ferromagnetic particle being reduced to the 0 required magnetic intensity that applies from the outside.Squareness ratio is residual magnetic flux and the ratio of saturated magnetic flux.It is the observed value of switch polar particle swarm under given magnetic intensity that switch yard distributes.Viscosity is to use #4 axles record under 50rpm and room temperature.
Table 4
Ex. Gloss Hc SR SFD VIm VOv
12 106 741 0.81 0.41 892 932
13 110 750 0.80 0.41 944 980
14 90 752 0.78 0.42 1350 1740
15 102 742 0.81 0.41 1480 1550
16 106 749 0.79 0.42 1700 1640
Embodiment 17
The mill base tackiness agent of iron content magnetic metal particle of the present invention prepares as follows:
The Alendronate solution that in 566.3 parts of (3.9mol) fused CHDM, adds 608.3 parts of embodiment 1,0.25 part of stannous oxalate catalyzer and 1169.2 parts of hexanodioic acids.Temperature maintenance stops the 195-200 ℃ of distillation until water.Then, after 140-150 ℃, add 1249.3 parts of CHDM again, be warming up to 195-200 ℃ again in reaction mixture.When distillation when stopping again, pressure is reduced to 45-50mmHg, reaction continued 1 hour in same temperature again, keep simultaneously column temperature in 50 ℃ to reduce to the loss of CHDM minimum.Add 0.5 part of catalyzer again, pressure is reduced to 20-25mmHg, is reflected at 195-200 ℃ and finishes reaction, can reach 0.99 and show by acid number.The OH value is 187.9.
Second kind of polyester that contains phosphonate of general procedure preparation by same just adding for the second time 1393.5 parts of CHDM.Acid number is 0.78, and the OH value is 214.1.
Preparation contains the blend of 61.4% the first phosphine acidifying polyester and 38.6% the second polyester, obtains a kind of OH value and be 198 polyester.Prepare urethane of the present invention.
By 665.3 parts of phosphine acidifying polyester copolymers, 665.3 parts of OH values are 198, from the 2-methyl isophthalic acid, the polyester that ammediol and hexanodioic acid make, and 69.6 parts of 2-methyl isophthalic acids, the mixture that ammediol is formed and 763.3 parts of MDI reacted 95 minutes, obtained urethane of the present invention.The viscosity of 15% (weight) mixed solvent (respectively containing equivalent MEK, CHO, and toluene) solution of this urethane is 270.The comparative example 3
The tackiness agent that is used for the comparison purpose is Zeon MR-110 vinylchlorid/vinyl-acetic ester/vinyl alcohol copolymer.Binder solution
Of the present invention, and the solution of the ethenyl adhesive of solution of above-mentioned polyurethane binder of embodiment 9 and prior art, all, 150.0 parts of tackiness agents make by being dissolved in mixed solvent.Mixed solvent respectively contains 340 parts of MEK, tetrahydrofuran (THF) and 170 parts of toluene.Mill base is made
Binder solution is used for the mill base prescription shown in the table 5.
Table 5
Composition Weight
Kanto Denka P1110B iron 1000.0
Carbon black (Regal 500R) 20.0
Aluminum oxide (Norton) 60.0
Methylethylketone 486.7
THF 486.7
Toluene 243.3
Hard ester acid 10.0
Binder solution 1000.0
The mill base enriched material is applied on the thick poly-terephthaldehyde's diethyl ester film of 36 μ m, and dry back thick coating 4 μ m measure embodiment 17, embodiment 9 and comparative example's 3 mill base is by behind the sand mill several times, the dispersive ability of every kind of mill base, coercive force, squareness ratio and switch yard distribute.The results are shown in table 6.
Table 6
Number of pass times MB Gloss Hc SR SFD
1 Ex9 98 1604 0.858 0.511
Ex17 86 1613 0.811 0.512
C.E.3 52 1604 0.813 0.524
2 Ex9 114 1590 0.828 0.501
Ex17 97 1619 0.830 0.504
C.E.3 58 1595 0.753 0.549
3 Ex9 118 1601 0.868 0.499
Ex17 99 1615 0.843 0.508
C.E.3 74 1583 0.779 0.542
4 Ex9 118 1606 0.868 0.501
Ex17 100 1615 0.853 0.511
C.E.3 75 1582 0.783 0.548
4+ hour Ex9 117 1592 0.835 0.523
Ex17 93 1608 0.806 0.549
C.E.3 53 1577 0.752 0.593
Annotate: Ex=embodiment
The C.E.=comparative example
Embodiment 18-21
By MDI with by MPD (2-methyl isophthalic acid, ammediol) or BEPD (2-butyl-2-ethyl-1, ammediol), the preparation of the reaction of the mixture that the MPD/ adipate polyester (MPDA) of phosphine acidifying polyester blend (PPB) and embodiment 17 is formed is a series of deionized, the urethane that contains phosphonate, wherein the weight ratio of PPB and MPDA is between 7: 93 to 40: 60.Chain extension agent, various polyester, and the parts by weight of MDI list in the table 7 list file names with the viscosity of various urethane in MEK/CHO/ toluene (1: 1: 1) wt mixed solvent and the viscosity of this solution of comparative example 2 urethane.
Table 7
Embodiment No. PPB MPDA MPD BEPD MDI Viscosity
18 93.1 1237.3 69.6 --- 760.4 40cps
19 188.3 1066.7 --- 145.0 761.3 48cps
20 399.1 931.3 69.6 --- 753.2 58cps
21 532.1 798.3 69.6 --- 750.2 88cps
The comparative example 2 --- --- --- --- --- 148cps
Mill base relatively
From each 215.9 parts of MEK, CHO and toluene (TOL) and 114.3 parts of embodiment 20 and 21 tackiness agent make binder solution, to be used for according to following formulation mill base construction:
Table 8
Composition Weight
Cobalt improved ferric oxide 1200.0
Carbon black 96.0
Aluminum oxide 24.0
Methylethylketone 401.5
Pimelinketone 313.3
Toluene 401.5
Tetradecanoic acid 9.0
Binder solution 761.9
The Brookfield viscosity of the mill base of embodiment 20 is 4550cps before grinding, is 12 after grinding by six times, and 900cps. (uses #6 axles are measured at 20rpm).
The Brookfield viscosity of the mill base of embodiment 21 is 2950cps before grinding, is 15 after grinding six times, 500cps.(all use #6 axles are measured at 20rpm).
Every kind of mill base solution all passes through mill several times on probation among the KDL.After passing through at every turn, all sample is applied on the thick poly terephthalic acid diethyl ester film of 36 μ m, make dried thick coating 4 μ m.
After passing through at every turn, the dispersive ability of the coating on the film, coercive force, data such as squareness ratio and switch yard distribution are listed in table 9.
Table 9
Number of pass times MB Gloss Hc SR SFD
1 20 46 749 0.762 0.486
21 40 743 0.762 0.491
2 20 87 757 0.803 0.447
21 87 758 0.807 0.450
3 20 92 749 0.791 0.451
21 95 758 0.808 0.447
4 20 97 754 0.811 0.448
21 102 759 0.817 0.441
5 20 101 752 0.816 0.445
21 104 754 0.817 0.436
6 20 102 754 0.806 0.445
21 106 755 0.818 0.439
6+ 24 hours 20 94 729 0.746 0.508
21 97 741 0.752 0.501
Embodiment 22-25 and comparative example's 4 magnetic recording compositions.
The preparation method that the deposition of the various tackiness agents of embodiment 18-21 makes up structure is as follows: at first 171.4 parts of tackiness agents are dissolved in by the MEK that respectively is 323.8 parts, in the solvent that CHO and TOL form, pass through then with 1142.9 parts of every kind of solution and by 69.1 parts of MEK, 13 parts of CHO, the solution that 69.1 parts of toluene and 9 parts of butyl myristates are formed mix and dilute various solution.Prepare the mill base construction according to the prescription in the above table 8 from the MR-110 tackiness agent.
Embodiment 22-25 that will make according to filling a prescription shown in the table 10 and comparative example 4 magnetic recording composition (MRC) are applied on the thick poly terephthalic acid diethyl ester film of 36 μ m, dry back thick coating 4 μ m.Glossiness and viscosity initial and for some time MRC afterwards are listed in table 11.Equally, coercive force (Hc), table 12 is listed in squareness ratio (SR) and switch yard distribution (SFD).
Table 10
Embodiment No. Mill base LDC18 LDC19 LDC20 LDC21 LDCCE2
22 403.5 163.9 ---- ---- ---- ----
23 401.0 ---- 162.9 ---- ---- ----
24 400.8 ---- ---- 162.9 ---- ----
25 400.9 ---- ---- ---- 162.9 ----
The comparative example 4 400.5 ---- ---- ---- ---- 162.7
LDC=deposits construction
Table 11
MRC Gloss Viscosity
Initial 24 hours Initial 30 minutes 24 hours
#6@ 20 #4@ 50 #6@ 20 #4@ 50 #6@ 20 #4@ 50
22 108 107 2100 960 2500 1090 3000 1270
23 114 114 2200 1040 2750 1180 3150 1300
24 117 118 2550 1140 2950 1220 3150 1300
25 117 118 2900 1260 3150 1300 3300 1360
CE4 102 97 3750 1770 5350 2240 6400 2720
Table 12
MRC Hc SR SFD
Initial 24 hours Initial 24 hours Initial 24 hours
22 767 759 0.818 0.802 0.427 0.454
23 764 751 0.822 0.788 0.427 0.454
24 762 747 0.819 0.794 0.435 0.458
25 762 745 0.830 0.792 0.440 0.461
CE4 759 751 0.813 0.779 0.441 0.487

Claims (8)

1. urethane resin tackiness agent that is used for magnetic recording medium is characterized in that it has mixed the functional group of following formula:
Figure C9510395000021
R wherein 1And R 2Can be identical or different, for having the alkoxyl group of 2-12 carbon atom, R 3Be the alkylidene group of 1-12 carbon atom, or the inferior aralkyl of 7-10 carbon atom, R 4Be the alkyl of 1-12 carbon atom, the cycloalkyl of 5-12 carbon atom, or the aryl of 6-12 carbon atom, wherein aryl can contain a halogen atom, hydroxyl or amino, and M +Be metal ion or ammonium ion.
2. resin glue as claimed in claim 1 is characterized in that R 1And R 2It is hydroxyethyl.
3. resin glue as claimed in claim 1 is characterized in that R 3It is methylene radical.
4. resin glue as claimed in claim 1 is characterized in that R 4It is ethyl.
5. magnetic recording medium, it is characterized in that, contain a kind of non-magnetic substrate and be applied to suprabasil a kind of magnetisable coating, this coating contains a kind of polyurethane binder resin and the magnetic-particle that is scattered in the resin, and this adhesive resin contains the functional group shown in the following formula:
Figure C9510395000022
R wherein 1And R 2Can be identical or different, for having the alkoxyl group of 2-12 carbon atom, R 3Be the alkylidene group of 1-12 carbon atom or the inferior aralkyl of 7-10 carbon atom, R 4Be the alkyl of 1-12 carbon atom, the cycloalkyl of 5-12 carbon atom, or the aryl of 6-12 carbon atom, wherein aryl can contain a halogen atom, hydroxyl or amino, and M +Be metal ion or ammonium ion.
6. magnetic recording medium as claimed in claim 5 is characterized in that R 1And R 2It is hydroxyethyl.
7. magnetic recording medium as claimed in claim 5 is characterized in that R 3It is methylene radical.
8. magnetic recording medium as claimed in claim 5 is characterized in that R 4It is the ethyl residue.
CN95103950A 1994-05-05 1995-04-12 Magnetic recording binder containing aminoalkylphosphonate salt Expired - Fee Related CN1090665C (en)

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Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6144525A (en) 1996-07-16 2000-11-07 Chang; Hao-Jan High density recording medium having a non-magnetic, metallic layer on a flexible substrate
JP4123538B2 (en) * 1997-03-04 2008-07-23 ソニー株式会社 Magnetic recording medium
AU6362100A (en) * 1999-07-23 2001-02-13 Children's Hospital Of Philadelphia, The Derivatized polyurethane compositions and methods of making
DE19945401C2 (en) 1999-09-22 2002-02-07 Emtec Magnetics Gmbh Binder composition containing fillers, process for their preparation and their use
JP2001101646A (en) * 1999-09-30 2001-04-13 Sony Corp Magnetic recording medium and method of manufacturing the same
JP2001126230A (en) 1999-10-29 2001-05-11 Sony Corp Magnetic recording medium and method of manufacturing the same
US7747730B1 (en) 2002-06-28 2010-06-29 Netfuel, Inc. Managing computer network resources
JP4891880B2 (en) * 2007-09-28 2012-03-07 富士フイルム株式会社 Surface modifier for ferromagnetic hexagonal ferrite powder and magnetic coating containing the same
CN101955746B (en) * 2010-10-15 2012-09-19 河海大学 Development of a polyester hot-melt adhesive for high-strength composite metal materials

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4637959A (en) * 1983-10-28 1987-01-20 Sony Corporation Magnetic recording medium
US5137951A (en) * 1990-04-06 1992-08-11 Ciba-Geigy Corporation Silylated hydroxyaminomethylphosphonates and stabilized compositions

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2635112A (en) * 1949-07-28 1953-04-14 Research Corp Process for producing aminomethylphosphonic acid compounds
CA1267987A (en) * 1984-08-02 1990-04-17 Union Carbide Corporation Phosphorylated reaction products and compositions incorporating such products
IT1199681B (en) * 1986-11-28 1988-12-30 Montedipe Spa POLYOLS-POLYESTERS AND THEIR USE IN THE PRODUCTION OF POLYURETHANE FOAMS
US5273826A (en) * 1988-10-28 1993-12-28 The B. F. Goodrich Company Magnetic coating formulations and magnetic recording media
JPH02128316A (en) * 1988-11-08 1990-05-16 Toyobo Co Ltd Magnetic recording medium
JP2584671B2 (en) * 1989-04-26 1997-02-26 富士写真フイルム株式会社 Photosensitive composition
JP2584672B2 (en) * 1989-04-28 1997-02-26 富士写真フイルム株式会社 Photosensitive composition
JPH02302929A (en) * 1989-05-17 1990-12-14 Fuji Photo Film Co Ltd Magnetic recording medium
US5164239A (en) * 1989-11-16 1992-11-17 Konica Corporation Magnetic disc assembly comprising a disc having a magnetic layer with a specified composition and a case having a specified liner
US5077329A (en) * 1990-04-06 1991-12-31 Ciba-Geigy Corporation Hydroxyaminomethylphosphonates and stabilized compositions

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4637959A (en) * 1983-10-28 1987-01-20 Sony Corporation Magnetic recording medium
US5137951A (en) * 1990-04-06 1992-08-11 Ciba-Geigy Corporation Silylated hydroxyaminomethylphosphonates and stabilized compositions

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KR950032349A (en) 1995-12-20
CN1113513A (en) 1995-12-20
US5556698A (en) 1996-09-17
DE69523979T2 (en) 2002-08-29
EP0681289A2 (en) 1995-11-08
US5681919A (en) 1997-10-28
TW343229B (en) 1998-10-21
CA2143353C (en) 1999-03-23
EP0681289B1 (en) 2001-11-21
ES2166801T3 (en) 2002-05-01
KR100186276B1 (en) 1999-05-15
JP2672783B2 (en) 1997-11-05
EP0681289A3 (en) 1997-07-09
JPH07302423A (en) 1995-11-14
DE69523979D1 (en) 2002-01-03
CA2143353A1 (en) 1995-11-06
AU664946B1 (en) 1995-12-07

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